JP2544788B2 - Deodorant synthetic fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a synthetic fiber having an excellent deodorizing property suitable for use in diapers, carpets, curtains, hospital sheets, and other applications where bad odor is disliked. It is about.

More specifically, ammonia is the main component of the rotting odor of meat, which is said to be one of the four major odors in the world, and basic gases such as trimethylamine, which is the main component of the rotting odor of fish, and the rotting of vegetables. A fiber that has excellent deodorizing performance against a wide range of malodorous components that are effective against acidic gases such as methyl mercaptan, which is the main component of odor, and hydrogen sulfide, which is the main component of rotten odor such as eggs and milk. Regarding

(Prior Art) Among synthetic fibers, polyester fibers, polyamide fibers and the like are indispensable as clothing materials in view of their excellent dimensional stability, chemical resistance, strength and durability. However, it has been desired to add a special function depending on the intended use. For example, hospital sheets, diapers,
In applications such as carpets that dislike bad odors, there has been a demand for a fiber product that retains the ability to reduce the bad odor that causes the odor as much as possible. Most of the conventional ones are natural needles, extracts from broad-leaved trees, extracts from green tea, etc. that are attached to the surface of textile products by post-processing methods, etc., but their durability is insufficient. There was a certain drawback. In particular, there has been a problem that the deodorant performance is extremely deteriorated when the laundry is repeatedly washed or the textile product is dyed.

As a deodorant type to be kneaded into a resin for the purpose of improving durability, there is a compound containing a divalent iron ion compound and L-ascorbic acid, but heat resistance is required for orientation in polyester. However, there is a problem in that it is insufficient, or when it is made into a textile product, it discolors after deodorizing a malodorous substance and can be used only for a specific purpose as a textile material.

Under these circumstances, the inventors of the present invention have made extensive studies to solve this problem, and have reached the present invention.

(Problems to be Solved by the Invention) That is, an object of the present invention is to add a deodorant to a fiber in order to fundamentally solve the above-mentioned drawbacks such as the conventional post-processing method of attaching the deodorant to the surface of the fiber. When making the fiber contained inside,
In order to make the fiber durable enough to be washed, etc., and effective in deodorizing a wide range of malodorous components, and not causing defects such as discoloration of textile products, what kind of material should be used? The present invention has clarified this point in terms of the structure and conditions.

(Means for Solving Problems) The synthetic fiber of the present invention comprises a thermoplastic polymer having a melting point of 150 ° C. or higher, such as polyester and / or polyamide,
It is a fiber having deodorant performance, characterized by containing 0.1 to 10% by weight of an inorganic fine powder having an excellent deodorant performance having an average particle diameter of 5 microns or less.

Hereinafter, the fiber of the present invention and the method for producing the same will be described in detail.

The inorganic fine particles used in the present invention preferably have an average particle diameter of 5 microns or less. If the particle size exceeds 5 μm, clogging of the filter and fluff breakage are likely to occur during melt spinning, making it difficult to use. In particular, when considering application to various clothing materials, bedding products, etc., fine denier yarn having a monofilament denier of about 1 denier is required, and if the particle size is large, yarn breakage during drawing becomes severe, which is not preferable. Therefore, the inorganic fine particles used in the present invention should have an average particle size of 5 microns or less.
It is more preferable that the diameter is 1 micron or less.

Inorganic fine particles used in the present invention, the ratio of zinc oxide and silicon dioxide in the range of 1: 5 to 5: 1 by weight ratio, has a mostly amorphous structure, substantially zinc silicate Amorphous fine particles are preferred. The ratio of zinc oxide and silicon dioxide is preferably in the range of 1: 4 to 4: 1, more preferably 1: 4.
A range of 3 to 3: 1 is preferred.

Zinc silicate is naturally produced in large amounts, but most have a crystalline structure. Surprisingly, when it has this crystal structure, almost no deodorant performance is exhibited. However, it has been found that excellent deodorizing performance is exhibited only by having a substantially amorphous amorphous structure, and that sufficient deodorizing performance is maintained even when contained and dispersed in the thermoplastic resin. . Moreover, even for basic gases such as ammonia and trimethylamines,
It has also been found that a good deodorizing effect is exhibited even with respect to acidic gases such as hydrogen sulfide and methyl mercaptan.

The substantially amorphous amorphous structure described here means a state in which substantially no crystal peak appears by X-ray diffraction analysis. That is, excellent deodorizing performance was exhibited.

Further, although the mechanism by which the inorganic fine particles of the present invention have a deodorant performance is not known at present, zinc oxide in zinc silicate causes a certain complex-forming reaction with respect to amphoteric basic gas and acidic gas. In addition to exerting the deodorizing effect, the physical adsorption effect of gas due to the amorphous structure of the inorganic fine particles is also exerted, and it is considered that the excellent deodorizing performance due to the synergistic effect is comprehensively expressed. It was further confirmed that, even when the inorganic particles are contained and dispersed in a thermoplastic polymer, and a fiber form obtained by using the inorganic particles is used, sufficient deodorizing performance is maintained. Normal,
When a deodorant is internally added to the resin, the deodorizing performance tends to be hindered and the effect tends to be reduced, and in particular, the deodorizing performance of acidic gas such as hydrogen sulfide is generally significantly reduced. However, when the inorganic fine particles of the present invention are internally added, the deodorizing performance is not deteriorated. The reason for this is not clear yet.

Further, the inorganic fine particles of the present invention are kneaded into, for example, polyethylene terephthalate polymer and made into a fiber, and the deodorant performance is maintained without being deteriorated even after being subjected to a high temperature dyeing treatment at 130 ° C. in a post-processing step. Wakatsuta. Furthermore, when the fiber is deodorized with a gas such as ammonia and then subjected to a washing treatment, the complex of the inorganic fine particles exhibiting the deodorizing performance and the deodorized gas molecule is broken, and the deodorizing gas component is washed off during the washing, and thus the fiber is removed. As a result, it was found that the deodorant performance was reproduced almost completely again, and by repeating the washing operation, it becomes possible to use it as a fiber that retains the deodorant performance, with virtually no life and semipermanently. Wakatsuta.

The amount of the inorganic fine particles of the present invention added to the thermoplastic polymer is preferably 0.1 to 10% by weight. More preferably 0.5-
10% by weight is good. When the amount added is less than 0.1%, it is difficult to say that the fiber has sufficient deodorizing performance. When the addition amount is 10% or more, the deodorizing performance is sufficient, but the processability during fiberizing is significantly deteriorated, which is not preferable. In particular,
During spinning, single yarn breakage and yarn breakage frequently occur due to stains around the nozzle holes, and the drawability is also significantly reduced, resulting in fluff,
Thread breaks occur frequently. Furthermore, the yarn path wear of the equipment during running of the yarn during the process is severely generated, which is not preferable.

The inorganic particles of the present invention are characterized by being a substantially amorphous substance of zinc silicate, and various methods for producing the inorganic particles are conceivable. For example, zinc oxide powder and silicon dioxide powder are used. It can also be manufactured by quantitatively mixing, then calcining at a high temperature, and then immediately rapidly pulverizing.

An example of measurement of deodorant performance is shown in FIG. In the case of ammonia, ammonia sensor 1 (AE-23 manufactured by Toa Denpa Co., Ltd.)
5), an ion meter 3 (IM-IE manufactured by Toa Denpa Co., Ltd.) and a recorder 4 are connected, and the change with time of the ammonia gas concentration in the container 5 is read. A predetermined amount of ammonia gas was put into the container 5 with a syringe, and then the measurement test 2
Set, and after leaving the ammonia concentration in the container for 2 hours,
It depends on the method of measurement.

For hydrogen sulfide, add a certain amount of sodium hydrogen sulfide, distilled water, and concentrated hydrochloric acid to a specified container to generate a certain amount of hydrogen sulfide gas, hang the measurement sample in the container, and store it at 25 ° C. Measurements were made after leaving for 24 hours using a Kitagawa gas detector tube.

The thermoplastic resin of the present invention is preferably a polymer having a melting point of 150 ° C. or higher and having excellent fiber-forming properties. Polyester or polyamide is particularly preferable.

Polyester is a polyester containing polyethylene terephthalate or polybutylene terephthalate as a main component, and terephthalic acid, isophthalic acid, naphthalene 2,6 dicarboxylic acid, phthalic acid, α, β- (4-carboxyphenoxy) ethane, 4 Aromatic dicarboxylic acid such as ′, 4′-dicarboxydiphenyl, 5-sodium sulfoisophthalic acid or adipic acid, aliphatic dicarboxylic acid such as sebacic acid, or esters thereof,
A fiber-forming polyester synthesized from a diol compound such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, polyethylene glycol or polytetramethylene glycol. A polyester in which 80 mol% or more, particularly 90 mol% or more of the units are polyethylene terephthalate units or polybutylene terephthalate units is preferable, and the melting point is
It is preferably 150 ° C or higher. When the melting point is low, the use as a fiber material for clothing is somewhat limited due to insufficient heat resistance and the like, which is not preferable. Further, the polyester may contain a small amount of additives, for example, a matting agent such as titanium oxide, an antioxidant, an optical brightener, a stabilizer or an ultraviolet absorber.

Polyamide is a polyamide whose main component is nylon 6, nylon 66, or meta-xylenediamine nylon, and may be a copolyamide containing a small amount of a third component, but the melting point may be maintained at 150 ° C or higher. preferable.

It goes without saying that the present invention can be expected to have the same effect with long fibers and short fibers.

The fiber of the present invention refers to a fiber constituting a woven fabric, a knitted fabric, a non-woven fabric or a processed product thereof, but a fiber other than the fiber, for example, natural fiber such as cotton, hemp and wool, general polyester, nylon, acrylic and the like. Synthetic fiber, and mixed woven fabric, such as acetate, rayon, and semi-synthetic fiber such as rayon,
It may be a mixed knitted fabric. In this case, the content ratio of the fiber of the present invention is preferably 30% or more, more preferably 50% or more from the viewpoint of deodorizing effect.

The fiber of the present invention, by high-order processing such as calcining crimping,
It has a shape similar to pentagonal or hexagonal, and has a multi-lobed shape such as trilobal, T-shaped, 4-lobe, 5-lobe, 6-lobe, 7-lobe, 8-lobe, etc. due to the irregular cross-section nozzle during spinning. The shape and various cross-sectional shapes can be taken, and the effect is sufficiently exhibited.

Next, a production example of the deodorant fiber of the present invention will be described. For example, in the case of polyethylene terephthalate fiber, a predetermined amount of the inorganic fine powder of the present invention is dispersed in ethylene glycol which is a monomer, and the primary particles are uniformly dispersed to an average of 5 microns or less by a vibration mill or a ball mill. There is a method in which powder-dispersed ethylene glycol is reacted with terephthalic acid under known conditions, then polymerized, and then fiberized. In this case, the polymerization rate becomes slow,
Occasionally a problem that the molecular weight does not increase to a predetermined degree of polymerization occurs, or the inorganic fine powder is likely to be thermally aggregated in the esterification step or the polymerization step, causing problems such as yarn breakage in spinning and drawing steps. Happens. A safer way is
This is a method of kneading a predetermined amount of inorganic fine particles of polyethylene terephthalate polymer finely pulverized to an average of 5 microns or less by a twin-screw kneading extruder or the like and re-pelletizing them to form fibers. In this case, a master polymer having a high content of inorganic fine particles may be prepared, and may be made into a fiber by diluting to a predetermined amount by a polymer blending method during spinning.

(Effect of the Invention) The fiber of the present invention has deodorant performance retained by containing zinc inorganic fine powder having excellent deodorant performance in the fiber. Moreover, the fiber of the present invention has a very long-lasting deodorant performance, and the deodorant performance does not deteriorate even after frequent washing, so that, for example, a hospital sheet, which is highly required to have wash resistance, Even when used in the field of diapers and the like, it is possible to exert sufficient deodorizing performance.

(Examples) The present invention will be specifically described with reference to examples. The washing conditions were as follows.

<Washing test method> Implemented in accordance with JIS L0217-103 method. 2 g per liter of water at a liquid temperature of 40 ° C
Add and dissolve a synthetic detergent for clothing at the ratio of to make a washing liquid. A sample and a load cloth are added to the washing liquid so that the bath ratio becomes 1:30, and the operation is started. After treating for 5 minutes, the operation was stopped, the test and load cloths were dehydrated with a dehydrator, and then the washing liquid was replaced with fresh water at room temperature, rinsed for 2 minutes with the same bath ratio, then dehydrated, and again with 2 Rinse for minutes and air dry. Repeat the above operation 10 times
It was used as a measurement sample after 10 times.

Example 1 A twin-screw kneading extruder manufactured by Japan Steel Works, Ltd. was used as a fine powder having an average particle size of 5 microns or less of zinc silicate having an amorphous structure and having a weight ratio of zinc oxide and silicon dioxide of 1: 3. Kneaded with polyethylene terephthalate resin using
A pellet containing wt% was obtained.

Then, the above inorganic fine powder containing 10 wt% pellets and ordinary polyethylene terephthalate pellets were blended at a ratio of 1: 4, fiberization was carried out, and inorganic fine powder having deodorant performance contained 2 wt% of fibers. Obtained. Spinning was performed at a spinning temperature of 290 ° C. and a winding speed of 1000 m / min, and then stretched by a roller plate method to obtain a multifilament of 75 denier 24 filament. The spinnability and drawability were good and there was no problem. After that, create a tubular knitted fabric by a conventional method,
After the relax, washing with water, drying and presetting, the deodorizing performance was measured.

10 g of the measurement sample was placed in an atmosphere kept at a 500 ppm ammonia concentration in a 2-liter container, and the ammonia concentration in the container after 2 hours was measured to calculate the deodorizing rate. After washing the JIS standard 10 times, the performance of the tubular knitted fabric was confirmed to be 90% or more of the ammonia deodorizing rate. In addition, the sample for which the ammonia deodorizing rate was once measured was washed, and the operation of measuring the ammonia deodorizing performance again in the same manner was repeated 5 times, but the 6th deodorizing rate was 90% or more. It has been confirmed that the same performance as the initial performance has reappeared.

Similarly, for hydrogen sulfide, place 10 g of the measurement sample in a hydrogen sulfide atmosphere held at 100 ppm in the container in 2 liters, measure the hydrogen sulfide concentration in the container after 24 hours, and measure the deodorization rate. I asked. After the JIS standard washes 10 times, the performance of the tubular knitted fabric was confirmed to be hydrogen sulfide deodorizing rate of 80% or more. Further, when the hydrogen sulfide was measured for the sixth time after repeating the operation 5 times (measurement → washing) in the same manner as the ammonia measurement, 80% or more of the deodorant performance was confirmed as in the initial performance.

Comparative Example 1 A zinc oxide fine powder having a crystal structure and an average particle size of 5 microns or less and a fine powder having a crystal structure and an average particle size of 5 microns or less were mixed at a weight ratio of 1: 3, and manufactured by Japan Steel Works, Ltd. It was kneaded with a polyethylene terephthalate resin using a twin-screw kneading extruder manufactured by the same company to obtain a pellet containing 10 wt% of the above inorganic fine powder in the polyethylene terephthalate resin.

Then, the inorganic fine powder 10 wt% containing pellets and ordinary polyethylene terephthalate were blended in a ratio of 1: 4, fiberization was carried out, and the inorganic fine powder having deodorant performance was 2 w.
A fiber containing t% was obtained. Spinning temperature 290 ℃, winding speed 10
Spinning was carried out at 00 m / min, and then drawing was carried out by a roller plate method to obtain a multifilament of 75 denier 24 filament. The spinnability and drawability were good and there was no problem. Then, a tubular knitted fabric was prepared by an ordinary method, and after relaxing, washing with water, drying and pre-setting, the deodorizing performance was measured.

In a 2-liter container, 10 g of a measurement test was placed in an atmosphere kept at an ammonia concentration of 500 ppm, the ammonia concentration in the container after 2 hours was measured, and the deodorizing rate was calculated. The initial performance and the performance of the tubular knitted fabric after the JIS standard washes 10 times were insufficient with the ammonia deodorizing rate of 35%. Further, the sample for which the ammonia deodorizing rate was once measured was washed, and the operation of measuring the ammonia deodorizing performance again in the same manner was repeated 5 times, and the 6th deodorizing rate was 35%.

Similarly, for hydrogen sulfide, a measurement sample was placed in a hydrogen sulfide atmosphere held at 100 ppm in a 2-liter container, the hydrogen sulfide concentration in the container was measured after 24 hours, and the deodorization rate was determined. . The initial performance and the performance of the tubular knitted fabric after the JIS standard washes 10 times were insufficient with a hydrogen sulfide deodorization rate of 25%. Further, when the hydrogen sulfide was measured for the sixth time after repeating the operation 5 times (measurement → washing) in the same manner as the ammonia measurement, the deodorizing rate was 25% as in the initial performance.

Examples 2 to 4 It was carried out under the conditions shown in Table 1. The same amorphous zinc silicate as in Example 1 was used, and the content in the fiber was changed. The content was changed by changing the blend ratio of pellets containing 10 wt% of amorphous zinc silicate fine powder and ordinary polyethylene terephthalate pellets. Other conditions were the same as in Example 1, and it was confirmed that all of them had good fiberizing processability and sufficient deodorizing performance.

Examples 5 and 6 Polymers used under the conditions shown in Table 1 were prepared using nylon 6 in Example 5 and polybutylene terephthalate in Example 6. In Example 5, a drawn yarn of 75 denier 24 filament was obtained by a spinning direct drawing method at a spinning temperature of 260 ° C. Example 6 has a spinning temperature of 260 ° C. and a winding speed of 1200 m / min.
Was spun and then drawn by a roller plate system to obtain a drawn yarn of 75 denier 24 filament. In all cases, the fiberizing processability was good, and the deodorizing performance was also good.

Examples 7,8 The mixing ratio of zinc oxide and silicon dioxide in amorphous zinc silicate was changed, and in Example 7, zinc oxide to silicon dioxide 1: 1,
Example 8 was performed 3: 1 and other conditions were the same as in Example 1. The fiberizing processability was good and the deodorizing performance was sufficient.

Comparative Example 2 A twin-screw kneading extruder manufactured by Japan Steel Works, Ltd. was used as a fine powder of zinc silicate having an amorphous structure with a weight ratio of zinc oxide and silicon dioxide of 1: 3 and having an average particle size of 5 microns or less. Kneaded with polyethylene terephthalate resin using
A pellet containing wt% was obtained.

Then, the above inorganic fine powder containing 10 wt% of pellets and ordinary polyethylene terephthalate pellets were blended at a ratio of 1: 199, fiberization was carried out, and the inorganic fine powder having deodorant performance contained 0.05 wt% of fibers. Obtained. Spinning temperature 290 ℃,
Spinning was carried out at a winding speed of 1000 m / min, and then stretching was carried out by a roller plate method to obtain a multifilament of 75 denier 24 filament. The spinnability and drawability were good and there was no problem. After that, a tubular knitted fabric was prepared by an ordinary method, and after relaxing, washing with water, drying, and pre-setting, the deodorizing performance was measured.

Comparative Example 3 A twin-screw kneading extruder manufactured by Japan Steel Works, Ltd. was used as a fine powder having an average particle size of 5 microns or less of zinc silicate having an amorphous structure and having a weight ratio of zinc oxide and silicon dioxide of 1: 3. Is mixed with polyethylene terephthalate resin, and the above inorganic fine powder is mixed in polyethylene terephthalate resin 15
A pellet containing wt% was obtained.

Next, when spinning was performed using the pellet containing 15 wt% of the inorganic fine powder, single yarn breakage and yarn breakage frequently occurred during spinning. The stretchability was also poor.

Comparative Examples 4 and 5 The mixing ratio of zinc oxide and silicon dioxide of amorphous zinc silicate was 15:85 in Comparative Example 4 and 85:15 in Comparative Example 5, and other conditions were the same as in Example 1. .

 The deodorizing performance was lower than that of Example 1.

Comparative Example 6 A zinc oxide fine powder having a particle size of 5 microns or less was prepared in Example 1.
In the same manner as described above, a twin-screw extruder was used to knead with a polyethylene terephthalate resin to obtain pellets containing 2.0% by weight of zinc oxide in the polyethylene terephthalate resin.

Spinning was performed using these pellets. The processability was good, but the level of deodorant performance was low.

[Brief description of drawings]

 FIG. 1 is a diagram showing an example of a deodorant performance measuring device. 1 …… Sensor 2 …… Measurement material (deodorant fiber structure) 3 …… Ion meter 4 …… Recorder 5 …… Container

Claims (1)

(57) [Claims] 1. Substantially amorphous inorganic fine particles of zinc silicate having an average particle size of 5 microns or less and having a ratio of zinc oxide to silicon dioxide of 1: 5 to 5: 1 and having a mostly amorphous structure. , 0.1 to 10 in a thermoplastic polymer with a melting point of 150 ° C or higher
Synthetic fiber having deodorant performance, characterized by being present in a weight percentage.